JP5721243B2 - Deoxidizing plastic material - Google Patents

Description

  The present invention initiates deoxygenation by providing a polyester composition comprising an organic compound, preferably an organic compound that is liquid at ambient temperature, a transition metal catalyst, and a polyamide to enhance the quality and shelf life of the oxygen sensitive product. On how to do. More specifically, the present invention relates to plastic materials and articles including polyesters and polyamides having excellent gas barrier properties and short or negligible deoxygenation induction periods.

  For the purposes of the present invention, a masterbatch (MB) is a composition comprising a polymeric carrier or liquid vehicle and an additive, where the additive is at a higher concentration than in the final application or final article. Present in and the carrier is a composition that need not be the organic polymer of the end use or final article. The preferred concentration of additives in the masterbatch is preferably in the range of 0.5 to 90% by weight, more preferably 1 to 80% by weight, each based on the total weight of the masterbatch.

  For the purposes of the present invention, a compound (CO) is a composition comprising an organic polymer and an additive, wherein the additive is present in the compound at a concentration desired for the final application or final article, and The organic polymer is the organic polymer of the final application or final article, so that the compound is simply made into the desired form of the final application or final article by a physical molding process. Composition.

  Packaging for personal care, medical, pharmaceutical, household, industrial, food and beverage needs a high barrier to oxygen and carbon dioxide to protect the freshness of the package contents. Containers made solely of glass or metal provide an excellent barrier to both the release of substances from the container and the entry of substances from the environment. In most cases, the gas permeability of glass or metal containers is negligible. Containers made entirely or partially of polymer generally do not have the shelf life or barrier properties of glass or metal containers. Many solutions have been proposed to overcome the problems associated with plastic containers. One material often used for packaging applications is polyethylene terephthalate resin (hereinafter referred to as PET). While PET has many advantageous properties for use in packaging applications, it does not have the gas barrier properties required or desirable for many applications. For example, PET has good oxygen barrier properties for carbonated soft drinks, but was not useful as a packaging material for other products such as beer that quickly loses flavor due to oxygen transfer into the bottle.

  Blends containing a small amount of a high barrier polyamide, such as poly (m-xylylene adipamide) (typically commercially known as MXD6), and a polyester such as PET enhance the passive barrier properties of PET. . To further reduce oxygen entry into the package contents, a small amount of transition metal salt is added to the blend of PET and polyamide to catalyze and actively promote the oxidation of the polyamide polymer, thereby increasing the oxygen barrier properties of the package. Can be strengthened.

  Deoxygenation of deoxygenating transition metals and many blends of polyamide and PET does not begin to any significant extent. The “induction period”, the time that elapses from the formation of an article and its filling until useful deoxygenation effectively begins and leads to a significant reduction in oxygen transmission, is the number of polyamide / cobalt salts in PET. In blends, these blends are long enough to enter the life cycle of the filled package before they are practically useless as deactive oxygenates. In some cases, the induction period is so long that no significant deoxygenation occurs before the package contents are consumed, so the induction period is no longer practically meaningful.

  US Pat. No. 5,021,515A, US Pat. No. 5,359,815A and US Pat. No. 5,955,527A to Cochran et al. Disclose the use of cobalt salts as the preferred transition metal catalyst and MXD6 as the preferred polyamide. It is stated that the oxygen scavenging properties of the composition appear only after aging, not immediately after blending. This delay, referred to as the induction period, can be as long as 30 days, which is due to costly aging techniques (long-term aging at normal temperature or aging accelerated at elevated temperature) or more It can be countered by a high concentration of oxidation catalyst.

  Much work has been done to increase the oxygen barrier properties of deoxygenating compositions and to minimize the corresponding induction period.

  Improved oxygen scavenging compositions based on transition metal / polyamide blends in PET are disclosed in US Pat. No. 5,302,430 A and EP 0 527 903 B1. In the initial literature, the long induction period typical for compositions comprising MXD6 and cobalt salts is attributed to the presence of phosphorus compounds that penetrate during the polyamide polymerization and / or are added during the stabilization phase. In the second document, the improvement in oxygen barrier properties is the “partially split or degraded” used, which is more sensitive to reaction with oxygen in the presence of metal ions compared to non-activated polyamides. degraded) "is believed to be due to activated groups in the polyamide.

  Another strategy for deoxygenation is to use a deoxygenating composition comprising an oxidizable ethylenically unsaturated hydrocarbon and a transition metal catalyst. US5310497A (patent document 6), US52111875A (patent document 7), US5346644A (patent document 8) and US5350622A (patent document 9) use poly (1,2-butadienes) as ethylenically unsaturated hydrocarbons. US Pat. No. 5,021,515A and US Pat. No. 5,211,875A disclose oxidizable polymers such as polyamide, polyisoprene, polybutadiene or copolymers thereof, in particular their block copolymers such as styrene- The use of butadiene is disclosed.

  It is known that deoxygenating compositions comprising an unsaturated polymer and a transition metal catalyst can be induced or activated by heat after forming a packaging article from the composition. Such a composition and method are disclosed in WO02 / 33024A2 (Patent Document 12). In these cases, the composition or article is expected to be immediately active and benefit from the described storage method.

  US5211875A and US5811027A disclose a method of minimizing the induction period of a deoxygenating composition by initiating deoxygenation through exposure to radiation. Both of these references rely on radiation containing UV or visible light (wavelengths containing UV radiation are preferred) and methods in the presence of photoinitiators to further facilitate or control deoxygenation initiation Teaches. Such UV initiator systems are particularly useful for deoxygenating compositions that include non-aromatic polymers. Although UV induction makes it possible to control when deoxygenation is initiated, the use of such methods that rely on UV radiation for induction of deoxygenation has limitations. First, the deoxygenating composition can include materials that are opaque to UV radiation, thus limiting the ability of UV radiation to activate deoxygenation. For example, deoxygenating compositions containing polymers such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) are difficult to induce using UV initiation because these polymers absorb UV light It is. Furthermore, due to the geometric and physical constraints associated with UV radiation, it can be difficult to achieve uniform UV treatment of preformed horned oxygen scavenging packaging articles.

US5021515A US5639815A US5955527A US5302430A EP0527903B1 US5310497A US521118A US5346644A US5350622A US5021515A US521118A WO02 / 33024A2 US521118A US5811027A US6509595B1

  There is a need for a quick onset of deoxygenation with an effective deoxygenating composition regardless of whether UV opaque material is present in the composition. It is also desirable to realize a method for initiating deoxygenation that is effective when a deoxygenating composition containing an aromatic polymer is used. An improved method for the uniform initiation of deoxygenation in a cornered packaging article would also be useful. In addition, it would be beneficial to provide deoxygenating compositions and packaging articles that do not require induction, such as induction by photoinitiators or heat treatment, for effective initiation of deoxygenation.

  Surprisingly, in polyester / polyamide compositions based on transition metals for the formation of articles such as plastic products for personal care products, medical products, pharmaceutical products, household products, industrial products, food and beverages, The use of inert organic compounds, preferably liquid organic compounds at ambient temperature, greatly improves deoxygenation performance compared to known transition metal based polyester / polyamide blends that do not contain inert liquid organic compounds, And a significant reduction or complete elimination of the deoxygenation induction period. An inert organic compound means that it does not react with components A to E under the production conditions described below.

The subject of the invention is a plastic material comprising a composition Z comprising the following components A, B, C and D, wherein component A is a polyester,
Component B is a polyamide,
Component C is a transition metal catalyst,
Component D is an organic compound selected from the group consisting of paraffins, vegetable oils, polyalkylene glycols, esters of polyols, alkoxylates and mixtures of these substances.

FIG. 1 is a diagram in which the amount of residual oxygen is plotted against the number of days elapsed.

  Preferably, component A is selected from the group consisting of polyesters resulting from the condensation reaction of dibasic acids and glycols. Typically, the dibasic acid comprises an aromatic dibasic acid, or an ester or anhydride thereof, and is isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6 -From the group consisting of dicarboxylic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, diphenoxyethane-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, and mixtures thereof Selected. The dibasic acid is an aliphatic dibasic acid or anhydride such as adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, fumaric acid, succinic anhydride, succinic acid, cyclohexanediacetic acid, glutaric acid, It can also be azelaic acid and mixtures thereof. Other aromatic and aliphatic dibasic acids known to those skilled in the art can also be used. More preferably, the dibasic acid comprises an aromatic dibasic acid, and optionally further comprises an aliphatic dibasic acid up to about 20% by weight of the dibasic acid component.

  Preferably, the glycol or diol component of the polyester is ethylene glycol, propylene glycol, butane-1,4-diol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,6-hexylene glycol, Pentane-1,5-diol, 3-methylpentanediol- (2,4), 2-methylpentanediol- (1,4), 2,2,4-trimethylpentane-diol- (1,3), 2 -Ethylhexanediol- (1,3), 2,2-diethylpropanediol- (1,3), hexanediol- (1,3), 1,4-di- (hydroxy-ethoxy) benzene, 2,2 -Bis- (4-hydroxycyclohexyl) propane, 2, -Dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis- (3-hydroxyethoxyphenyl) propane, 2,2-bis- (4-hydroxypropoxyphenyl) propane, 1,4-dihydroxy Selected from the group consisting of methyl-cyclohexane, and mixtures thereof. Additional glycols known to those skilled in the art may also be used as the glycol component of the polyester.

  Two preferred polyesters are polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). PET and PEN are homopolymers or copolymers further comprising up to 10 mol% of dibasic acids different from terephthalic acid or naphthalene dicarboxylic acid and / or up to 10 mol% of glycols different from ethylene glycol. Can be.

  The PEN is preferably polyethylene naphthalene 2,6-dicarboxylate, polyethylene naphthalene 1,4-dicarboxylate, polyethylene naphthalene 1,6-dicarboxylate, polyethylene naphthalene 1,8-dicarboxylate, and polyethylene naphthalene 2 , 3-dicarboxylate. More preferably, the PEN is polyethylene naphthalene 2,3-dicarboxylate.

  More preferably, component A is PET, such as virgin bottle great PET and postconsumer PET (PC-PET), cyclohexanedimethanol / PET copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT). , And mixtures thereof.

  The polyester of component A preferably has an intrinsic viscosity of 0.4 dl / g to 2.0 dl / g, more preferably 0.5 to 1.5 dl / g, even more preferably 0.7 to 1.0 dl / g. Have The intrinsic viscosity was measured under the following conditions: 3.8 g of polyester powder under vacuum application at 150 ° C. for 8 to 12 hours, die length 1.269 cm, die diameter 0.0508 cm, treatment temperature 295 ° C. , Using a Davenport Melt Viscosimeter.

Preferably component B is selected from the group consisting of aliphatic polyamides and partially aromatic polyamides. The number average molecular weight M _n of the polyamide is preferably 1000 to 45000, more preferably 3000 to 25000.

The aliphatic polyamide can be a fully aliphatic polyamide and can comprise a moiety of —CO (CH 2) _n CONH (CH 2) _m NH— or a moiety of — (CH 2) _p CONH—. , N, m and p are each independently an integer ranging from 1 to 10, preferably ranging from 4 to 6. Preferably, aliphatic polyamides include poly (hexamethylene adipamide), poly (caprolactam) and poly (hexamethylene adipamide) -co-caprolactam. The aliphatic polyamide is in particular poly (hexamethylene adipamide) -co-caprolactam.

  In the sense of the present invention, “partially aromatic polyamide” is polymerized from a mixture of aromatic and non-aromatic monomers or precursors. Preferably, the partially aromatic polyamide is isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, aliphatic diacid having 6 to 12 carbon atoms and meta- or para-xylenediamine, 1,3- or 1, Polyamides formed from 4-cyclohexane (bis) methylamine, aliphatic diamines having 4 to 12 carbon atoms, or aliphatic amino acids having 6 to 12 carbon atoms, or all possible combinations of 6 to 6 carbon atoms It is selected from the group consisting of polyamides formed from 12 lactams, or polyamides formed from other commonly known diacids and diamines that form polyamides. Partially aromatic polyamides may also contain trifunctional or tetrafunctional comonomers such as trimellitic anhydride, dianhydropyromellitic acid, or other polyacids and polyamines known in the prior art to produce polyamides.

  More preferably, the partially aromatic polyamide is poly (m-xylylene adipamide), poly (hexamethylene isophthalamide), poly (hexamethylene adipamide-co-isophthalamide), poly (hexamethylene). Selected from the group consisting of adipamide-co-terephthalamide) and poly (hexamethyleneisophthalamide-co-terephthalamide).

  Even more preferably, the polyamide is poly (m-xylylene adipamide).

  Preferably, component C is an oxidizable component, such as a transition metal catalyst active in the oxidation of polyamide, and accelerates the deoxygenation rate. The mechanism by which this transition metal activates or accelerates the oxidation of the polyamide polymer is not clear. The catalyst may or may not be consumed in the oxidation reaction, or if consumed, will only be consumed temporarily by being converted to a catalytically active state. As described in US Pat. No. 5,955,527A, some amount of catalyst may be lost in side reactions, or the catalyst can be considered as an initiator that generates free radicals. Through the branch chain reaction, deoxygenation is unbalanced with the amount of catalyst.

  More preferably, catalyst C is in the form of a salt with a transition metal selected from the first, second or third transition series of the periodic table. Suitable metals and their oxidation states include, but are not limited to, manganese II or III, iron II or III, cobalt II or III, nickel II or III, copper I or II, rhodium II, III or IV, and ruthenium Etc. The oxidation state of the metal when introduced need not necessarily be that of the active form. The metal is preferably iron, nickel, manganese, cobalt or copper; more preferably manganese or cobalt; even more preferably cobalt. Preferred counter ions for the metal include, but are not limited to, chloride, acetate, propionate, oleate, stearate, palmitate, 2-ethylhexanoate, neodecanoate or naphthenate. The metal salt can also be an ionomer, in which case a polymeric counter ion is used. Such ionomers are well known in the art.

  Even more preferably, the salt, transition metal and counterion are compliant with national regulations for food contact materials or, if part of the packaging article, are packaged from a deoxygenating composition. There is virtually no movement to the content that has been made. Particularly preferred salts include cobalt oleate, cobalt propionate, cobalt stearate, and cobalt neodecanoate.

  Preferably component D is liquid at ambient temperature, ie 20-30 ° C. and atmospheric pressure. “Liquid” means a dynamic viscosity of 0.2 to 104 mPas, preferably 1 to 5000 mPas, measured at 20 ° C. with a rotation viscosimeter.

The paraffin or mineral oil is preferably a liquid C _5-19 hydrocarbon. The vegetable oil is preferably selected from the group consisting of castor oil, soybean oil, linseed oil and rapeseed oil.

  Polyalkylene glycols include polymers of alkylene oxides. The polyalkylene glycol can be in the form of a homopolymer, or a mixture or combination of homopolymers, or can it include a copolymer, such as a block or random copolymer, or a mixture or combination of such copolymers? Or a mixture or combination of a homopolymer and a copolymer. Preferably, the polyalkylene glycol is selected from the group consisting of polyethylene glycol, polypropylene glycol and ethylene / propylene glycol copolymers and has a molecular weight of 200 to 600 g / mol.

  Examples of polyol esters include glycol esters, polyalkylene glycol esters, glycerol esters, polyglycerol esters, sorbitan esters, sucrose esters, and polyoxyalkylene polyol esters. Preferably, the polyol ester is selected from the group consisting of polyalkylene glycol esters, glycerol esters, sorbitan esters. Preferably, the polyalkylene glycol ester is selected from the group consisting of polyethylene glycol esters, polypropylene glycol esters, or esters of ethylene / propylene glycol copolymers. More preferably, the polyalkylene glycol ester is selected from the group consisting of polyethylene glycol esters, more preferably from the group consisting of polyethylene glycol monolaurate and dilaurate, and polyethylene glycol monooleate and dioleate, wherein the polyethylene glycol moiety ( PEG) has an average molecular weight of 600 g / mol or less.

  The glycerol ester is preferably a fatty acid ester of glycerol. The fatty acid ester of glycerol is preferably selected from the group consisting of monoacylglycerol, diacylglycerol, and triacylglycerol obtained by esterifying glycerol with one, two or three saturated or unsaturated fatty acids. More preferably, the monoacylglycerol is esterified with acetic acid, lactic acid, succinic acid and citric acid. The sorbitan ester is preferably a fatty acid ester of sorbitol. The fatty acid ester of sorbitol is preferably selected from the group consisting of monoacyl sorbitol, diacyl sorbitol, and triacyl sorbitol obtained by esterifying sorbitol with one, two or three saturated or unsaturated fatty acids. More preferably, the fatty acid ester of sorbitol is selected from the group consisting of sorbitan monolaurate, sorbitan monooleate and sorbitan trioleate.

Alkoxylates are alkylenes on substrates such as linear or branched primary or secondary C ₁₂ -C ₁₈ alcohols, ie natural or synthetic fatty alcohols, alkylphenols, fatty acids, fatty acid ethanolamides, fatty amines, fatty acid esters and vegetable oils. It is obtained by adding an oxide. The degree of alkoxylation, i.e. the molar ratio of added alkylene oxide per mole of substrate, varies in a wide range, generally from 3 to 30, and is selected depending on the intended use. Preferably, the alkylene oxide is ethylene oxide. More preferably, the ethoxylate is selected from the group consisting of ethoxylated vegetable oils, ethoxylated esters of vegetable oils, and ethoxylated sorbitan esters. Even more preferably, ethoxylates, polyoxyethylene in each molecule _{- (CH 2 CH 2 O)} - , wherein the total number of groups is 4 to 20, ethoxylated castor oil, ethoxylated sorbitan oleate And ethoxylated sorbitan laurate.

Optionally, composition Z comprises one or more further substances (component E), which are natural colorants derived from plants or animals, and synthetic colorants, here preferred synthetic colorants Is a synthetic organic or inorganic dye or pigment,
-Preferred synthetic organic pigments are azo or disazo pigments, lake azo or disazo pigments or polycyclic pigments, particularly preferably phthalocyanine, diketopyrrolopyrrole, quinacridone, perylene, dioxazine, anthraquinone, thioindigo, diaryl or quinophthalone pigments. Yes;
-Preferred synthetic inorganic pigments are metal oxides, mixed oxides, aluminum sulfates, chromates, metal powders, pearlescent pigments (mica), luminescent colorants, titanium oxides, cadmium lead pigments, iron oxides, carbon black Silicates, nickel titanates, cobalt pigments or trivalent chromium;
Fillers and nanosize fillers, preferably silica, zeolites, silicates, particularly preferably aluminum silicates, sodium silicates, calcium silicates, chalk or talc; metal hydrates;
Auxiliaries, preferably acid scavengers, processing aids, coupling agents, lubricants, stearates, foaming agents, polyhydric alcohols, nucleating agents, or antioxidants, such as stearates, or oxides, such as Magnesium oxide;
An antioxidant, preferably a primary or secondary antioxidant;
-Antistatic agents;
-Compatibilizers for polyester / polyamide blends;
UV absorbers, slip agents, anti-fogging agents, anti-condensation agents, suspension stabilizers, anti-blocking agents, waxes, and mixtures of these substances,
Selected from the group consisting of

  More preferably, component E is selected from the group consisting of compatibilizers, antioxidants and colorants for polyester-polyamide blends.

  Because of the good refractive index match between PET and poly (m-xylylene adipamide) (MXD6), a clear blend is obtained, almost like PET. However, fogging was observed with biaxially stretched films and stretch blow bottles. The incompatibility between PET and MXD6 leads to large MDX6 particles, which can effectively scatter light. Compatibilization of the polyester / polyamide blend with compatibilizer E reduces the particle size to sub-micron levels, thus providing a container with greatly improved impact peel resistance, adhesion, color and transparency.

  Preferred compatibilizers include, but are not limited to, polyester ionomers, preferably PET ionomers, isophthalic acid (IPA) modified PET, p-toluenesulfonic acid (pTSA) modified PET, dianhydropyromellitic acid (PMDA) modified PET, and Examples include malic anhydride-modified PET. Other preferred compatibilizers include acrylic modified polyolefin type ionomers and low molecular weight bisphenol-A epoxy resins-E44, which can be added directly to the PET / polyamide blend. In addition, trimellitic anhydride (TMA) is added to the polyamide, transesterified, mixed with PET, and then a bifunctional coupler such as, but not limited to, diphenylmethane-4,4-diisocyanate (MDI), diphenylmethane-4,4. -Coupling can be performed using diisopropyl urethane (DU) or bisoxazoline (BOX). If a compatibilizer is used, preferably one or more properties of the polyamide / polyester blend are improved, including, for example, color, haze, and blends. There is adhesion between the layer and the layer containing polyester.

  Preferred polyester ionomers include those disclosed in US6500895B1 (Patent Document 15). Preferred PET ionomers include sulfonated PET. One preferred modified PET type compatibilizer is IPA modified PET.

Preferably, the composition Z is
80 to 98.9% by weight of component A;
1 to 10% by weight of component B;
0.0001 to 0.8% by weight of component C;
0.01 to 2% by weight of component D;
0 to 18.9899%, preferably 0 to 18% by weight of component E;
More preferably -90 to 98% by weight of component A;
1-7% by weight of component B;
-0.001 to 0.5% by weight of component C;
0.1 to 2% by weight of component D;
0 to 8.899% by weight of component E;
Wherein the weight percentages are each based on the total weight of composition Z, and the weight percentages of components A, B, C, D and E are always 100% in total.

  When component E is present, the lower limit is 0.001% by weight, preferably 0.01% by weight, based on the total weight of composition Z.

  The plastic material of the present invention is suitably molded into a plastic article, for example blow molded.

  Therefore, another subject of the present invention is a molded plastic article comprising the above plastic material. Yet another subject of the invention is a molded plastic article made of a plastic material consisting of composition Z.

  The molded article of the present invention is a packaging material, preferably a container, film or sheet, especially personal care products, cosmetics, medical products, pharmaceuticals, household products, industrial products where a high oxygen barrier is required. These articles can be for use in food and beverage packaging. Wrapping materials suitable for containing the oxygen scavenging composition Z can be flexible, rigid, semi-rigid or some combination thereof. Rigid packaging articles typically have a wall thickness in the range of 100 to 1000 micrometers. A typical flexible wrap typically has a wall thickness of 5 to 250 micrometers.

  Preferably, the containers in which the composition Z is used for deoxygenation, such as bottles, films and sheets, are monolayers. The packaging article or film comprising the oxygen scavenging composition of the present invention may consist of a single layer or may comprise multiple layers. If the packaging article or film includes an oxygen scavenging layer, it can further include one or more additional layers, one or more of these additional layers including an oxygen barrier layer. Contains or is oxygen permeable. Still other additional layers, such as adhesive layers, can be used in multi-layer packaging articles or films.

  Another subject of the invention is a method for producing the plastic material or article as described above, wherein the components A, B, C, D, optionally and E are physically mixed together and subjected to a molding process. It is the said method characterized by the above-mentioned.

For physical mixing, conventional mixing equipment in the plastics industry can be used. Preferably, the mixing device can be that used to produce a liquid masterbatch or a solid masterbatch, or it can be a combination of these devices. The mixing device for the liquid masterbatch can be a high speed disperser (eg of the Cowles ^™ type), a media mill, a three roll mill, a submill or a rotor-stator type disperser. The mixing equipment used to produce solid masterbatch MB or compound CO is: mixer, extruder, kneader, press, mill, calendar, blender, injection molding machine, injection and stretch blow molding machine (ISBM), extrusion Blow molding machine (EBM), compression molding machine, compression and stretch blow molding machine; more preferably mixer, extruder, injection molding machine, injection and stretch blow molding machine, compression molding machine, compression and stretch blow molding machine; Preferred are mixers, extruders, injection and stretch blow molding machines, and extrusion blow molding machines.

  The molding process of the article depends on the desired shape of the article to be manufactured. The container is preferably made by a blow molding, injection molding, injection and stretch blow molding, extrusion blow molding, compression molding, compression and stretch blow molding process. Films and sheets are preferably cast or blown film extrusion or coextrusion processes, and finally finally thermoformed or stretched, depending on the required thickness and the number of layers required to obtain specific properties. Manufactured by a simple post-extrusion process. In a thermoforming process, a plastic sheet is heated to a molding temperature that facilitates molding, molded into a specific shape in a mold, and trimmed into a final article. If vacuum is used, this method is commonly referred to as vacuum forming. In the post-extrusion stretching process, the extruded film can be biaxially oriented, for example, by drawing. All of the above processes are well known in the art.

  In the case of composition Z comprising more than one masterbatch or component, the extruder may be equipped with a metering system for introducing the component and / or masterbatch into the mainstream polymer. This metered addition may be done directly with one or more pure ingredients or with one or more masterbatches.

  The type of metering device used depends on the form of the pure ingredients or masterbatch when metered.

  In the case of solid components, a feed screw type metering device is usually used and the point of introduction may be at the main inlet of the extruder together with the main polymer granule feed or located along the extruder. It can be a non-pressurized charging zone. In the case of a solid masterbatch, the metering device may be a system that includes an additional extruder that pre-melts the masterbatch, pressurizes it, and meteres it using a metering pump. The amount of masterbatch added is advantageously supplied without pressure and from a point along the main extruder. In the case of a liquid pure ingredient or liquid masterbatch, the metering device either introduces the liquid masterbatch with the main polymer granule feed from the main inlet of the extruder without pressure or by extrusion. It may be a system that includes one or more metering pumps that are introduced at points of pressure located along the machine.

  The polyester / polyamide blends used in the present invention include the production of polyesters and polyamides by known methods. The polyester and polyamide are dried separately or in combination, in an atmosphere of dry air or dry nitrogen, or under reduced pressure. Instead of the melt compound, the polyester and polyamide may be dry blended and thermoformed or pultruded into a plastic article. Alternatively, the polyamide polymer can be added to the melt phase polymerization for the production of the polyester, preferably at a later stage in the production of the polyester. In order to avoid or limit the number of reactions that may contribute to the generation of unwanted colors or lead to degradation of the polyamide, the polyamide may be added at the end of the melt phase reaction process, for example at the end of the finishing reaction. It can be added to the finisher, or it can be added after the melt phase production is complete and before the molten product is placed in the die of the melt processing equipment used to make the pellets.

  Mixing the components to produce composition Z can be done in one step, two steps or multiple steps. Components A, B, C, D, optionally and E are directly metered and / or diluted down, for example in injection and stretch blow molding machines, in the form of liquids or solid concentrates or as pure components. Mixing can be done in one step. Mixing can also take place in two or three steps, in which case in the first step components C, D, optionally and D are predispersed in each other, and in one or more subsequent steps, Add to components A and B. It is preferred to first obtain a masterbatch containing components C and D and then combine this masterbatch with components A and B. In one preferred embodiment, the first masterbatch is liquid and consists of components C, D, optionally and E. In another preferred embodiment, the first masterbatch is solid and consists of C, D, optionally E, and A. In either case of a two-step or three-step mixing process, it is most preferred that component B is added to or added to component B in the last step.

  In one preferred embodiment of the invention, in the first step, component C, optionally and E, are dispersed in component D to provide a liquid buster batch. In the second step, the liquid masterbatch is metered and diluted into a stream of polyester A, optionally and component E, via a metering pump. For example, in a single or twin screw extruder, after melt compounding, the extrudate is withdrawn in the form of strands and recovered as pellets according to conventional methods such as cutting. In the third step, the resulting solid masterbatch is subjected to salt and pepper like polyamide pellets and polyester pellets, one or both of which may optionally be pulverized, for example in an injection and stretch blow molding machine by a converter / compander. Metered and diluted into the main stream of the blend of or metered and diluted into the main stream of the polyester / polyamide concentrate.

  In another aspect of the invention, in a first step, component C, optionally and component E, are dispersed in component D to provide a liquid masterbatch. In the second step, this liquid masterbatch is metered and diluted in a stream with component B, optionally and component E, via a metering pump. For example, in a single or twin screw extruder, after melt compounding, the extrudate is withdrawn in the form of strands and recovered as pellets according to conventional methods such as cutting. In a third step, the solid masterbatch obtained is converted by a converter / compound into a polyester mainstream, for example a polyester mainstream of an injection and stretch blow molding machine, at a rate corresponding to the desired final polyamide concentration in the article and Weigh and dilute without a separate metering step of polyamide.

  In another preferred embodiment of the invention, in the first step, components C, D, optionally and component E are dispersed in component A to provide a solid masterbatch. In the second step, the solid masterbatch obtained is converted into salt and pepper of polyamide pellets and polyester pellets, for example in an injection and stretch blow molding machine, by a converter / compounder, one or both of which may optionally be ground. Metered and diluted into the mainstream of such blends, or metered and diluted into the mainstream of polyester / polyamide concentrate.

  In another aspect of the present invention, in the first step, components C, D, optionally and component E are dispersed in component B to provide a solid masterbatch. In the second step, the resulting masterbatch is converted by a converter / compound into a polyester mainstream, for example a polyester mainstream of an injection and stretch blow molding machine, at a rate corresponding to the desired final polyamide concentration in the article. Weigh and dilute without a separate metering step.

  In another preferred embodiment of the invention, component C, optionally and component E are dispersed in component D in a first step to provide a liquid masterbatch and in a second step the liquid master The batch is made into a main stream of salt and pepper like blends of polyamide pellets and polyester pellets, optionally one or both of which may be crushed, via metering pumps, by a converter / compander, for example in injection and stretch blow molding machines. Metered and diluted or metered and diluted into the main stream of polyester / polyamide concentrate.

  Mixing is preferably continuous or batchwise, more preferably continuous; in the case of solid masterbatches MD, preferably by extrusion, mixing, milling or calendering, more preferably extrusion; liquid masterbatches In the case of MB, it is preferably carried out by mixing or milling; in the case of compound CO, it is preferably carried out by extrusion or calendering, more preferably by extrusion.

  Mixing is preferably performed at a temperature of 0 to 330 ° C. The mixing time is preferably 5 seconds to 36 hours, preferably 5 seconds to 24 hours. The mixing time in the case of continuous mixing is preferably 5 seconds to 1 hour. The mixing time in the case of batch mixing is preferably 1 second to 36 hours.

  In the case of the liquid master batch MB, the mixing is preferably performed at a temperature of 0 to 150 ° C. and a mixing time of 0.5 to 60 minutes. In the case of solid masterbatch MB or compound CO, the mixing is preferably carried out at a temperature of 80 to 330 ° C. for a mixing time of 5 seconds to 1 hour.

  The preferred article of the present invention is a hollow container, which is purposely manufactured by any type of blow molding process known in the art. Blow molding of thermoplastic hollow containers is conventionally performed by blow molding of extruded thermoplastic polymeric parison (extrusion blow molding-EBM) or thermoplastic polymeric preform (which is usually injection molded from a thermoplastic polymer). ) Blow molding (injection and stretch blow molding-ISBM). The hot thermoplastic polymeric parison or heated preform is contained within the mold cavity where the pressurized gas provides blow molding of the container into the shape of the mold cavity.

  ISBM processes are generally divided into two main types. The first type is a one-step process in which a preform is molded and conditioned and then transferred to a stretch blow molding operation before the preform cools below its softening temperature. The second type of ISBM process is a two-step process, in which the preform is pre-manufactured and stored for later use. In the two-step process, the preform is reheated before the start of the stretch blow molding step. This two-step process has the advantage of faster cycle times because the stretch blow molding step does not depend on the slower injection molding operation to be completed. However, the two-step process has the problem of reheating the preform to the stretch blow molding temperature. This is usually done using infrared heating, which provides radiant energy outside the preform. It is sometimes difficult to uniformly heat a preform using this technique, and if not done carefully, large temperature gradients can occur from the outside of the preform to the center. Usually, the conditions must be carefully selected so that the inside of the preform is heated to an appropriate molding temperature without overheating the outside. After all, a two-step process usually has a smaller operating window than a one-step process.

  In order to measure the deoxygenation capacity of the present invention, the deoxygenation rate can be calculated by measuring the time that elapses before an article depletes a predetermined amount of oxygen from a sealed container. For example, the film containing the deoxygenated component can be placed in an oxygen-containing atmosphere, such as an airtight sealed container of air typically containing 20.6% by volume oxygen. Next, over a period of time, a sample of the atmosphere inside the container is taken out, and the residual oxygen ratio is obtained.

  For active oxygen barrier applications, the combination of oxygen barrier and any deoxygenation activity is less than about 0.1 cubic centimeter per liter of package per day at 25 ° C. when the average container thickness is about 250 micrometers. It is preferable to provide an overall oxygen transmission rate. It is also preferred that the oxygen scavenging capacity is such that the permeation rate is not exceeded for at least two days.

  Another definition of acceptable deoxygenation is derived from testing actual packaging. In actual use, the deoxygenation rate requirement is highly dependent on the internal atmosphere of the package, the contents of the package, and the temperature at which it is stored. In actual use situations, it has been found that the deoxygenation rate of the deoxygenated article or package should be sufficient to maintain an increase in internal oxygen levels below 1 ppm over a period of about 4 weeks.

  The deoxygenation capacity of an article comprising the present invention can be measured by determining the amount of oxygen consumed before the article is no longer effective as a deoxygenate.

In actual use, the deoxygenation capacity of the article is determined by the three parameters of each application: the amount of oxygen initially present in the package,
The rate of oxygen penetration into the package when it is not deoxygenated, and the intended shelf life of the package,
Depends heavily on

  For purposes of the present invention, the deoxygenation performance of various compositions may be compared based on the following empirical formula.

X · t _max = Y
Here, for a given oxygen scavenging composition and / or a given article,
X is defined as the maximum oxygen content measured over a 100 day observation period,
t _max is defined as the time that elapses from the formation of the article and its filling until the oxygen content X reaches its maximum value;
Y gives an indication of the degree of deoxygenation efficiency and induction characteristic of that deoxygenating composition.

  When comparing articles containing different deoxygenating compositions and having different deoxygenating capabilities, the higher the Y value, the lower the deoxygenating performance of the corresponding composition and article.

  The composition Z enables the use of transition metal based polyester-polyamide blends as deoxygenation systems with sufficiently improved deoxygenation performance and reduced induction times.

  The advantage of using a deoxygenating composition obtained by adding organic compound D to a transition metal based polyester / polyamide composition as compared to a similar composition without organic compound D is: Indicated by oxygen absorption measurements made on various systems. Surprisingly, in the presence of inert organic compound D, a significant reduction or complete elimination of the induction period is more effective due to the lower residual oxygen concentration that is maintained throughout the shelf life of the product. Observed with high deoxygenation activity. More surprisingly, when the transition metal salt pre-dispersed in the liquid organic compound D is added to the mainstream of polyester and polyamide when manufacturing the article, it has excellent oxygen barrier properties and negligible degree. A composition having an induction time is provided.

  Furthermore, these unexpected behaviors are compared to the amounts required for transition metal based polyester / polyamide blends that do not contain organic compound D in order to obtain the necessary or comparable deoxygenation activity in the final polyester article. Thus, a smaller amount of polyamide can be used.

Test methods Product characteristics are measured in the following manner, unless otherwise stated:
The density value is measured according to ASTM D792 (g / cm ³ ).

  The melt flow rate (MFR) value is measured according to ASTM D1238 (g / 10 min at specific temperature and weight).

Deoxygenation activity measurement method:
For a typical carbonated beverage shelf life test, (i) in a nitrogen circulating glove box, fill a 500 ml volume bottle with deoxygenated water until the headspace is 10 ml (where the bottle contains (Ii) up to 2.8 volumes of carbonic acid (ie, the amount of gas dissolved per 1 cm ^{3 of} water is 2.8 cm ³ ). Carbonate with CO ₂ and then cap. Next, the oxygen concentration in the empty upper space of the bottle is measured using a nondestructive oxygen measuring sensor and a Fibox (registered trademark) transmitter. Data is collected in parallel for at least two bottles of the same composition at regular time intervals and over a 100 day time frame. For each sample bottle, the oxygen entry at a certain time is calculated as the difference between the oxygen content measured at that time and the oxygen concentration measured at time zero. The oxygen intrusion is then averaged with the number of sample bottles measured for each composition and then plotted against time.

  The weight percentages described in the following examples are based on the total weight of the mixture, composition or article. Parts are parts by weight.

  Unless otherwise stated, “ex” indicates an example, “cpex” indicates a comparative example, and MB indicates a master batch.

Used substance component A1:
Polyethylene terephthalate (PET) having a density of 1.35 to 1.45 g / cm ³ and an intrinsic viscosity of 0.74 to 0.78 dl / g (ASTM D3236-88)
Component A2:
Polybutylene terephthalate (PBT) having a density of 1.28 to 1.32 g / cm ³ and an intrinsic viscosity of 0.90 to 1.00 dl / g (ASTM D3236-88)
Component B1:
Poly (m-xylylene adipamide) (MXD6) having a density of 1.20 to 1.30 g / cm ³ and an MFR of 2 g / 10 min (measured at 275 ° C./0.325 kg)
Component C1:
Cobalt stearate (cobalt concentration 9.5%)
Component C2:
Cobalt neodecanoate (cobalt concentration 20.5%)
Component D1:
Sorbitan monooleate component D2 having a density of 0.98 to 1.02 g / cm ³ at 20 ° C. and a hydroxyl number (DIN 53240) of up to 220 mg KOH / g:
White mineral oil component E1: having a density of 0.85-0.88 g / cm ³ at 15 ° C. and a viscosity (ASTM D445) of 66-74 mm ² / s at 40 ° C.
Acid value (ASTM D664) of 24-29 mg KOH / g and 7000-9500 mPascal. isophthalic acid modified polyethylene terephthalate having an ICI corn & plate melt viscosity (ASTM D4287)

Masterbatch MB1-MB8
Each component was homogenized with a Leistritz® ZSE18HP extruder at a temperature of 230 ° C. to obtain solid masterbatches MB1, MB2, MB7 and MB8. Liquid master batches MB3 to MB6 were obtained by stirring each component for 15 minutes without any intended heating in a Cowles mixer. Table 1 shows the details.

ex1 to ex7 and cpex1 to cpex3:
Component A1 was dried at 160 ° C. for 7 hours, then the other components were homogenized and mixed in the proportions listed in Table 2. The resulting compounds CO1-CO10 were used for the production of 500 ml bottles via a two-step ISBM process. First, a 23 g preform was produced on an injection molding machine Arburg (registered trademark) 420C 1000-150, then cooled to room temperature, and then subjected to a stretch blow molding step with Sidel (registered trademark) SBO-1.

  As an example of the operation mode, using Arburg (registered trademark) 420C 1000-150, component A1 pre-dried at 160 ° C. for 6 hours is charged into the main hopper of an injection molding machine, and other components (MB1 to MB8). And / or B1) was added via a metered addition unit applied to the main stream of component A1 before entering the injection unit barrel, to obtain a preform by injection molding. The barrel temperature can be maintained at a temperature of 270-295 ° C. and the cycle time can be varied between 14-16 seconds.

  The weight of the preform is selected according to standard preforms on the market and can be set, for example, to 23 g per preform. The mold can be cooled with water, eg, 8 ° C. water. After being removed from the mold, the preform can be collected for continuous blow molding by using a Sidel® SBO-1 blow molding unit.

  This unit, for example with a mold for a 500 ml (nominal volume) bottle, includes a heating zone where the preform is heated to a variable temperature in the preform and final bottle design; the final temperature of the preform is 105-110 The preform is then charged into a bottle mold and blown by injecting dry air or nitrogen with a pressure profile reaching a maximum of 35-40 bar; It takes 3 seconds.

  The average production rate was 900 bottles / hour.

  The blow molded bottle is then collected from the blow molding unit for the necessary tests.

  The corresponding deoxygenation activity was then measured according to the method described above. The resulting graphical representation is shown in Graph 1; the corresponding numerical data is reported in Table 3.

  CO10 consists of a transition metal-based polyester / polyamide composition prepared according to the prior art and is therefore free of organic compound D. CO4 is produced by mixing various components according to Table 3, but polyamide is not used.

Measured data and empirical formula defined here, ie
X · t _max = Y
Accordingly, compositions CO1-CO10 clearly showed different deoxygenation performance, where lower Y values were recorded for compositions CO2, CO5, CO6, CO7, CO8 and CO9 of the present invention. A low Y value indicates both good deoxygenation performance and shortened induction time. Table 4 gives details of each composition.

Claims (12)

A plastic material comprising a composition Z comprising components A, B, C and D,
Component A is a polyester selected from the group consisting of polyethylene terephthalate, cyclohexanedimethanol / polyethylene terephthalate copolymer, polyethylene naphthalate, polybutylene terephthalate, and mixtures thereof ;
Component B is poly (m-xylylene adipamide), poly (hexamethylene adipamide), poly (hexamethylene adipamide-co-isophthalamide), poly (hexamethylene adipamide-co-terephthalamide) Selected from the group consisting of: poly (hexamethylene isophthalamide-co-terephthalamide), poly (hexamethylene adipamide), poly (caprolactam), poly (hexamethylene adipamide) -co-caprolactam, and mixtures thereof a polyamides,
Component C is a transition metal catalyst selected from the group consisting of cobalt oleate, cobalt propionate, cobalt stearate, cobalt neodecanoate, and mixtures thereof;
Component D is an organic compound selected from the group consisting of paraffins, vegetable oils, esters of polyols, and mixtures of these substances.
Said plastic material. The plastic material according to claim 1, wherein component D is liquid at ambient temperature and atmospheric pressure. Composition Z further comprises component E, which is component E
Colorants, fillers, acid scavengers, processing aids, coupling agents, lubricants, stearates, foaming agents, polyhydric alcohols, nucleating agents, antioxidants, antistatic agents, compatibilizers for polyester / polyamide blends 3. A plastic according to claim 1 or 2 selected from the group consisting of UV absorbers, slip agents, anti-fogging agents, anti-condensation agents, suspension stabilizers, anti-blocking agents, waxes and mixtures of these substances. material. Composition Z is
80 to 98.9% by weight of component A;
1 to 10% by weight of component B;
0.0001 to 0.8% by weight of component C;
0.01 to 2% by weight of component D;
0 to 18.9899% by weight of component E;
Where the weight percent is based on the total weight of composition Z and the weight percent of components A, B, C, D and E is always 100% in total.
The plastic material as described in any one of Claims 1-3 . The plastic material according to any one of claims 1 to 4 , which is in the form of a molded plastic article. 6. The plastic material of claim 5 , wherein the molded plastic article is a container, sheet or film. The plastic material according to claim 5 or 6 , for use in packaging foods, beverages, cosmetics, pharmaceuticals or personal care products. The plastic material according to claim 6 or 7 , wherein the container is a bottle. Component A, B, C, D, and optionally E are physically mixed with one another, and characterized in that subjected to the molding process, plastic material according to any one of claims 1-8 Manufacturing method. The method of claim 9 , wherein the mixing comprises extrusion, kneading, milling or calendering. 11. A method according to claim 9 or 10 , wherein the molding process comprises blow molding, injection molding, injection and stretch blow molding, extrusion blow molding, compression molding, compression, stretch blow molding, cast or film extrusion. 12. In any one of claims 9-11 , wherein in a first step, components C, D, optionally and E are predispersed in each other and added to components A and B in one or more subsequent steps. The method according to one.

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